CN105675831A - Apparatus and method for measuring chlorine ion and total organic carbon in water - Google Patents
Apparatus and method for measuring chlorine ion and total organic carbon in water Download PDFInfo
- Publication number
- CN105675831A CN105675831A CN201510758412.6A CN201510758412A CN105675831A CN 105675831 A CN105675831 A CN 105675831A CN 201510758412 A CN201510758412 A CN 201510758412A CN 105675831 A CN105675831 A CN 105675831A
- Authority
- CN
- China
- Prior art keywords
- sample
- water
- organic carbon
- gas
- detector
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000005070 sampling Methods 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 239000013535 sea water Substances 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 5
- 239000010865 sewage Substances 0.000 claims abstract description 3
- 239000002352 surface water Substances 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 19
- 241000370738 Chlorion Species 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 238000004448 titration Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000003918 potentiometric titration Methods 0.000 claims description 6
- 238000001745 non-dispersive infrared spectroscopy Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 230000003321 amplification Effects 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 230000002572 peristaltic effect Effects 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002910 solid waste Substances 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 2
- 239000003651 drinking water Substances 0.000 abstract description 2
- 235000020188 drinking water Nutrition 0.000 abstract description 2
- 238000005259 measurement Methods 0.000 abstract 3
- 239000010842 industrial wastewater Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 235000011089 carbon dioxide Nutrition 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 230000036284 oxygen consumption Effects 0.000 description 6
- 230000020477 pH reduction Effects 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000012417 linear regression Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical class [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1826—Organic contamination in water
- G01N33/1846—Total carbon analysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/182—Specific anions in water
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides an apparatus for measuring chlorine ion and total organic carbon in sea water, high-chlorine and -salt wastewater, surface water, underground water, drinking water, domestic sewage and industrial wastewater, wherein the apparatus mainly includes a sample quantitative sampling device, a potentiometric titrator, a horizontal rotor, a sample dish, a sample cup (sample tube), an automatic sample injector, a multi-position valve, an oxidization reactor, a gas-liquid separator, a membrane filter and a detector, and a data processing and display apparatus. The apparatus can be used for measuring the chlorine ion and the total organic carbon in water for measurement in laboratories, on-line measurement and emergent portable in-site measurement.
Description
Technical field
The present invention relates to a kind of water quality analyzer device, it is a kind of device measuring chlorion and total organic carbon in water specifically.
Background technology
Total organic carbon (TOC, TotalOrganicCarbon) as the index of organic pollutants, become the main means of world many countries water treatment and quality control, it is widely applied to the quality control of the aspects such as rivers, lake and Marine monitoring. The Carbon flux analysis of drinking water supply, pharmacy, food, semi-conductor industry, refuse humification degree analyzing, aquatic system, the mensuration of soil carbon content and the carbon cycle of soil all need to carry out the mensuration of TOC.
Existing TOC automatic analyser, when for measuring seawater and high-salt wastewater, due to Cl-Interference, monitoring CO2Content time, bigger error can be produced; For this reason, mainly have employed reduce sample size, pre-dilution, with mercury salt-solution absorption, with KI solution or hydroxylamine hydrochloride solution wash, connection metal paper tinsel etc. before detector. Such as the TOC analyser of certain company, employing be reduce sample size mode so that the chlorion that the seawater sample making more trace produces is not enough to affect the measured value of TOC. But owing to the method sample introduction needle core is meticulous, even if water sample being carried out essence filter, repeatedly clean again after entering sample, the problem of nook closing member blocking still often occurs; Water sample is carried out beforehand dilution, is compare conventional method at present, it is intended that make Cl by dilution-Concentration be reduced to the degree being not enough to carbonic acid gas detected result produces interference, but for seawater and high-salt wastewater, often Cl-Concentration far away higher than the concentration of TOC, if extension rate is excessive, the concentration of TOC is possibly lower than the detection limit of instrument; Cl uses mercury salt-solution absorption, although can be eliminated more thoroughly-Interference, but discharge waste liquid in containing severe toxicity Hg, secondary pollution can be produced; The hydroxylamine hydrochloride solution washing reaction gas method that the KI solution of external report and " Marine monitoring specification " GB17378-2007 propose, because technique is too complicated, can only be used for interval and measure and cannot be used for continuous on-line determination; The TOC determinator of offshore company, have employed the method for connection metal paper tinsel in front of the detector and absorbs Cl-Ion, but owing to absorbing Cl-The ability of ion is very limited, it is necessary to constantly change, and is still not enough to eliminate completely seawater and high-salt wastewater Cl-Interference.
Patent of invention publication number was CN102564823A (application number 201110433551.3) before carbonic acid gas detects, and installs the ion hydrazine containing silver and absorbs chlorine and form solid, reduces or eliminates the interference of chlorine, but can not measure the concentration of chlorion.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide the determinator of chlorion and total organic carbon in a kind of seawater, high chlorine high-salt wastewater, the surface water, underground water, tap water, sanitary sewage, trade effluent and method, can be used for experimental determination, on-line determination, emergent portable field mensuration.
In mensuration water provided by the invention, the device of chlorion and total organic carbon, mainly comprises sample amounts sampling unit, potentiometric titrator; Horizontal rotor, sample disc, sample cup (sample hose); Automatic sampler, multi-position valve, oxidation reactor, gas-liquid separator, film filter, detector; Data processing and display unit.
Foregoing device, it is preferable that scheme be that described quantitative sampling device is peristaltic pump, quantitatively syringe, quantitative loop; When measuring for field portable, CO2 removal cleaner can be installed before quantitative sampling device.
Foregoing device, preferred scheme is, after described automatic sampler software programming and micro-chip, PLC, data collecting card, stepper-motor, servomotor realize titration being completed according to sample cup (sample hose) physical location, carry out supernatant fluid be separated with throw out after supernatant fluid sample.
Foregoing device, it is preferable that scheme be that described potentiometric titrator is for carrying out potentiometric titration to liquid in the sample cup (sample hose) of different positions, it is possible to be automatical potentiometric titrimeter, it is also possible to titration manually. After titration completes, horizontal rotor rotates, it is achieved supernatant fluid is separated with throw out; The automatic control of potentiometric titration is realized with software programming and micro-chip, PLC, data collecting card, stepper-motor, servomotor.
Foregoing device, it is preferable that scheme be, described horizontal rotor connect sample disc, sample disc is placed with one or more sample cups (sample hose); The shape of horizontal rotor and sample disc can be circle, tetragon, Polygons or irregular shape. Realize moving at a certain distance or rotating with software programming and micro-chip, PLC, data collecting card, stepper-motor, servomotor, to realize the needs of potentiometric titration and automatic sampler.
Foregoing device, it is preferable that scheme be that described multi-position valve can be 2 logical valves, 3 logical valves, 6 logical valves, 10 logical valves etc.
Foregoing device, preferred scheme is, described oxidation reactor is dry method high temperature combustion oxidation device, middle temperature catalyticcombustion oxidizer, Ultraviolet Oxidation device, ozone oxidation device, microwave oxidizer, light wave oxidizer, ultrasound oxidation technology device, supercritical oxidation device, carbon fiber oxidizer, secondary oxidizer or device are by titanium dioxide, persulphate, platinum, hydrogen peroxide or the Fenton class oxygenant that is made up of ferrous iron and hydrogen peroxide, it is possible to be one or more combinations of above method; Use high purity oxygen gas, high pure air, rare gas element, nitrogen as carrier gas.
Foregoing device, preferred scheme is, described detector is infrared detector (NDIR), Conductivity detection instrument, plasma atomic emission spectrometer, laser gas analyzer, hydrogen flameionization method detector, coulomb analyser, ultraviolet spectroscopy and carries out gathering amplification to optical signal by photomultiplier, and converts the combination of one or more detectors of the detector of the analysis process system of electrical signal to.
Foregoing device, it is preferable that scheme be, described sample amounts sampling unit, potentiometric titrator;Horizontal rotor, sample disc, sample cup (sample hose); Automatic sampler, multi-position valve, oxidation reactor, gas-liquid separator, film filter, detector; Data processing and display unit can be combined into 1 analytical system device and use, it is also possible to separation is analyzed separately to measure and used.
Foregoing device, preferred scheme is, the device of chlorion and total organic carbon in described mensuration water, it is possible to for solid matter such as soil, solid waste, solid article etc., gas, after being manipulated so water sample, measures the concentration of chlorion, total organic carbon (TOC).
Present invention also offers the method that the device described in utilization measures chlorion and total organic carbon in water, step is:
1. the mensuration of chlorine ion concentration and precipitate and separate: aqueous sample stream to be measured removes foreign material through filter, by sample amounts sampling unit, enter sample disc, there is magnetic stirrer bottom sample disc, in the sample cup in sample disc, have stirrer, when automatic potentiometer moves in this sample cup, rotary magnet in magnetic stirrer starts to rotate, driving the stirrer in sample cup to rotate, make liquid mixing even, the reaction of this precipitation titration is as follows:
Ag++CI-→AgCI↓
When arriving terminal, by the change directing terminal of current potential, it is achieved the precipitate and separate of chlorion.
Sample disc or automatic sampler rotate automatically, until one or more testing samples are titrated; Subsequently, sample disc is driven by horizontal rotor and carries out high speed rotating, carries out centrifugation, it is achieved supernatant fluid and precipitate and separate.
The mensuration of 2.TOC concentration: an automatic sampler institute sample thief part enters acidification reactor, acidification reactor adds acid solution (such as phosphoric acid solution), inorganic carbon such as sodium carbonate, sodium bicarbonate and acid-respons is made to decomposite carbonic acid gas, detector measures gas concentration lwevel, with organic carbon concentration in minusing calculation sample, or the carbonic acid gas that inorganic carbon is produced directly discharges.
Na2CO3+2H+→2Na++H2O+CO2↑
NaHCO3+H+→Na++H2O+CO2↑
Automatic sampler institute sample thief another part enters oxidation reactor, make total organic carbon generation oxidizing reaction in sample, produce carbonic acid gas, by gas-liquid separator, after film filter, enter detector and measure gas concentration lwevel, extrapolating organic carbon concentration in sample according to gas concentration lwevel, organic carbon concentration stores in a database, shows at upper computer (display screen) simultaneously, or by network, it is transferred to remote display.
Total organic carbon oxidizing reaction formula is:
CnHn+O2→CO2+H2O
Organic carbon concentration (TOC) and chemical oxygen demand (COD) (COD) concentration show simultaneously
One is that COD is the oxygen (O consumed theoretically2), representing oxygen-consumption, TOC represents oxygen-consumption, then COD=K*TOC with carbon (C), because C+O2=CO2, so K=32/12=2.67.
Two is the linear regression theory using organic carbon concentration (TOC) and chemical oxygen demand (COD) (COD), according to Y=a+bX, measure the series concentration of TOC and COD respectively, extrapolate the concentration of chemical oxygen demand (COD) (COD), accomplish to show organic carbon concentration (TOC) and chemical oxygen demand (COD) (COD) concentration over the display simultaneously;
Accompanying drawing explanation
Fig. 1 be embodiment 1 online/experimental determination water in the structural representation of device of chlorion and total organic carbon
Wherein, 1-sample amounts sampling unit; The automatic potentiometer of 2-; 3-sample disc (horizontal rotor); 4-automatic sampler; 5-multi-position valve; 6-oxidation reactor; 7-gas-liquid separator; 8-film filter; 9-detector; 9-1. electrical conductivity detector; 9-2.NDIR infrared detector;10-data handler; 11-indicating meter; 12. network data transmission devices; 13-acidification reactor;
Embodiment
Explanation of nouns horizontal rotor is the horizontal rotor on whizzer, work characteristics:
1, when horizontal rotor is static, the centrifuge tube medullary ray in rotor is parallel with turning axle.
2, when horizontal rotor rotates and accelerates, centrifuge tube medullary ray is transitioned into turning axle close to vertical position gradually by parallel position.
3, when speed falls in horizontal rotor, centrifuge tube medullary ray tends to parallel position by with turning axle gradually close to vertical position.
The technical scheme of the present invention is described in detail below in conjunction with embodiment and accompanying drawing, but protection domain is not by this restriction.
Embodiment 1 is online/experimental determination water in the device of chlorion and total organic carbon, accompanying drawing 1:
(1) mensuration of chlorine ion concentration and precipitate and separate: aqueous sample stream to be measured removes foreign material through filter, by 1. sample amounts sampling units, enter 3. sample disc, there is magnetic stirrer bottom sample disc, in the sample cup in sample disc, have stirrer, when 2. automatic potentiometers move in this sample cup, rotary magnet in magnetic stirrer starts to rotate, driving the stirrer in sample cup to rotate, make liquid mixing even, the reaction of this precipitation titration is as follows:
Ag++CI-→AgCI↓
When arriving terminal, by the change directing terminal of current potential, it is achieved the precipitate and separate of chlorion.
3. sample disc or 4. automatic samplers rotate automatically, until one or more testing samples are titrated; Subsequently, 3. sample disc is driven by horizontal rotor and carries out high speed rotating, carries out centrifugation, it is achieved supernatant fluid and precipitate and separate.
(2) mensuration of TOC concentration: a 2. automatic sampler institute sample thief part enters 13. acidification reactors, 13. acidification reactors add acid solution (such as phosphoric acid solution), inorganic carbon such as sodium carbonate, sodium bicarbonate and acid-respons is made to decomposite carbonic acid gas, 9. detector measures gas concentration lwevel, with organic carbon concentration in minusing calculation sample, or the carbonic acid gas that inorganic carbon is produced directly discharges.
Na2CO3+2H+→2Na++H2O+CO2↑
NaHCO3+H+→Na++H2O+CO2↑
4. automatic sampler institute sample thief another part enters 6. oxidation reactors, make total organic carbon generation oxidizing reaction in sample, produce carbonic acid gas, by 7. gas-liquid separators, 8. after film filter, enter 9. detectors and measure gas concentration lwevel, in 10. data handlers, organic carbon concentration in sample is extrapolated according to gas concentration lwevel, organic carbon concentration is stored in database or file, show in 11. indicating meters simultaneously, or by 12. network data transmission devices, it is transferred to remote display.
Total organic carbon oxidizing reaction formula is:
CnHn+O2→CO2+H2O
Organic carbon concentration (TOC) and chemical oxygen demand (COD) (COD) concentration show simultaneously
One is that COD is the oxygen (O consumed theoretically2), representing oxygen-consumption, TOC represents oxygen-consumption, then COD=K*TOC with carbon (C), because C+O2=CO2, so K=32/12=2.67.
Two is the linear regression theory using organic carbon concentration (TOC) and chemical oxygen demand (COD) (COD), according to Y=a+bX, measure the series concentration of TOC and COD respectively, extrapolate the concentration of chemical oxygen demand (COD) (COD), accomplish to show organic carbon concentration (TOC) and chemical oxygen demand (COD) (COD) concentration over the display simultaneously;
Embodiment 2 is the device that emergent portable field measures:
(1) mensuration of chlorine ion concentration and precipitate and separate: water sample to be measured adds 3. sample disc manually or automatically, 3. there is magnetic stirrer bottom sample disc, 3. there is stirrer in the sample cup in sample disc, when 2. automatic potentiometers move in this sample cup, rotary magnet in magnetic stirrer starts to rotate, driving the stirrer in sample cup to rotate, make liquid mixing even, the reaction of this precipitation titration is as follows:
Ag++CI-→AgCI↓
When arriving terminal, by the change directing terminal of current potential, it is achieved the precipitate and separate of chlorion.
3. sample disc 4. automatic sampler rotates automatically, until one or more testing samples are titrated; Subsequently, 3. sample disc is driven by horizontal rotor and carries out high speed rotating, carries out centrifugation, it is achieved supernatant fluid and precipitate and separate.
(2) mensuration of TOC concentration: a sampler sample thief part enters 13. acidification reactors manually or automatically, 13. acidification reactors add acid solution (such as phosphoric acid solution), inorganic carbon such as sodium carbonate, sodium bicarbonate and acid-respons is made to decomposite carbonic acid gas, 9-1. electrical conductivity detector or 9-2.NDIR infrared detector measure gas concentration lwevel, with organic carbon concentration in minusing calculation sample, or the carbonic acid gas that inorganic carbon is produced directly discharges.
Na2CO3+2H+→2Na++H2O+CO2↑
NaHCO3+H+→Na++H2O+CO2↑
4. sampler institute sample thief another part enters 6. oxidation reactors manually or automatically, make total organic carbon generation oxidizing reaction in sample, produce carbonic acid gas, by 7. gas-liquid separators, 8. after film filter, enter 9-1. electrical conductivity detector or 9-2.NDIR infrared detector mensuration gas concentration lwevel, in 10. data handlers, organic carbon concentration in sample is extrapolated according to gas concentration lwevel, organic carbon concentration is stored in database or file, show in 11. indicating meters simultaneously, or by 12. network data transmission devices, it is transferred to remote display.
Total organic carbon oxidizing reaction formula is:
CnHn+O2→CO2+H2O
Organic carbon concentration (TOC) and chemical oxygen demand (COD) (COD) concentration show simultaneously
One is that COD is the oxygen (O consumed theoretically2), representing oxygen-consumption, TOC represents oxygen-consumption, then COD=K*TOC with carbon (C), because C+O2=CO2, so K=32/12=2.67.
Two is the linear regression theory using organic carbon concentration (TOC) and chemical oxygen demand (COD) (COD), according to Y=a+bX, measure the series concentration of TOC and COD respectively, extrapolate the concentration of chemical oxygen demand (COD) (COD), accomplish to show organic carbon concentration (TOC) and chemical oxygen demand (COD) (COD) concentration over the display simultaneously.
Claims (10)
1. seawater, high chlorine high-salt wastewater, the surface water, underground water, tap water, sanitary sewage, the determinator of chlorion and total organic carbon in trade effluent, it is characterized in that, mainly comprise sample amounts sampling unit, potentiometric titrator; Horizontal rotor, sample disc, sample cup (sample hose); Automatic sampler, multi-position valve, oxidation reactor, gas-liquid separator, film filter, detector; Data processing and display unit, can be used for experimental determination, on-line determination, emergent portable field mensuration.
2. device according to claim 1, is characterized in that, described sample amounts sampling unit, is peristaltic pump, quantitatively syringe, quantitative loop; When measuring for field portable, CO2 removal cleaner can be installed before quantitative sampling device.
3. device according to claim 1, is characterized in that, described potentiometric titrator is for carrying out potentiometric titration to liquid in the sample cup (sample hose) of different positions, it is possible to be automatical potentiometric titrimeter, it is also possible to titration manually. After titration completes, horizontal rotor rotates, it is achieved supernatant fluid is separated with throw out; The automatic control of potentiometric titration is realized with software programming and micro-chip, PLC, data collecting card, stepper-motor, servomotor.
4. device according to claim 1, is characterized in that, described horizontal rotor connects sample disc, is placed with one or more sample cups (sample hose) in sample disc;The shape of horizontal rotor and sample disc can be circle, tetragon, Polygons or irregular shape. Realize moving at a certain distance or rotating with software programming and micro-chip, PLC, data collecting card, stepper-motor, servomotor, to realize the needs of potentiometric titration and automatic sampler.
5. device according to claim 1, it is characterized in that, after described automatic sampler software programming and micro-chip, PLC, data collecting card, stepper-motor, servomotor realize titration being completed according to sample cup (sample hose) physical location, carry out supernatant fluid be separated with throw out after supernatant fluid sample.
6. device according to claim 1, is characterized in that, described multi-position valve can be 2 logical valves, 3 logical valves, 6 logical valves, 10 logical valves etc.
7. device according to claim 1, it is characterized in that, described oxidation reactor is dry method high temperature combustion oxidation device, middle temperature catalyticcombustion oxidizer, Ultraviolet Oxidation device, ozone oxidation device, microwave oxidizer, light wave oxidizer, ultrasound oxidation technology device, supercritical oxidation device, carbon fiber oxidizer, secondary oxidizer or device are by titanium dioxide, persulphate, platinum, hydrogen peroxide or the Fenton class oxygenant that is made up of ferrous iron and hydrogen peroxide, it is possible to be one or more combinations of above method; Use high purity oxygen gas, high pure air, rare gas element, nitrogen as carrier gas.
8. device according to claim 1, it is characterized in that, described detector is infrared detector (NDIR), Conductivity detection instrument, plasma atomic emission spectrometer, laser gas analyzer, hydrogen flameionization method flame ionization ditector, coulomb analyser, ultraviolet spectroscopy and carries out gathering amplification to optical signal by photomultiplier, and converts the combination of one or more detectors of the detector of the analysis process system of electrical signal to.
9. device according to claim 1, is characterized in that, described sample amounts sampling unit, potentiometric titrator; Horizontal rotor, sample disc, sample cup (sample hose); Automatic sampler, multi-position valve, oxidation reactor, gas-liquid separator, film filter, detector; Data processing and display unit can be combined into 1 analytical system device and use, it is also possible to separation is analyzed separately to measure and used.
10. device according to claim 1, it is characterized in that, the device of chlorion and total organic carbon in described mensuration water, may be used for solid matter if soil, solid waste, solid article etc. and gas are after being manipulated so water sample, measure the concentration of chlorion, total organic carbon (TOC).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510758412.6A CN105675831A (en) | 2015-11-08 | 2015-11-08 | Apparatus and method for measuring chlorine ion and total organic carbon in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510758412.6A CN105675831A (en) | 2015-11-08 | 2015-11-08 | Apparatus and method for measuring chlorine ion and total organic carbon in water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105675831A true CN105675831A (en) | 2016-06-15 |
Family
ID=56946884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510758412.6A Pending CN105675831A (en) | 2015-11-08 | 2015-11-08 | Apparatus and method for measuring chlorine ion and total organic carbon in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105675831A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106290316A (en) * | 2016-08-16 | 2017-01-04 | 湖北兴发化工集团股份有限公司 | A kind of analysis method of Dimethyldichlorosilane hydrolysate intermediate ion |
| CN106338945A (en) * | 2016-10-14 | 2017-01-18 | 王杨 | Intelligent electronic semi-finished product detection apparatus |
| CN112461991A (en) * | 2019-09-06 | 2021-03-09 | 荆门市格林美新材料有限公司 | Method and device for rapidly detecting metal yield of battery material |
| CN112526099A (en) * | 2020-12-11 | 2021-03-19 | 江苏源泉智能装备科技有限公司 | High-chlorine wastewater COD detection device and method |
| WO2021231073A1 (en) * | 2020-05-12 | 2021-11-18 | University Of Washington | Apparatus and method for measurement of halogens in samples |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4248598A (en) * | 1978-05-30 | 1981-02-03 | Blunck Otto H | Process and apparatus for the determination of the contents of organically bound carbon in water containing organic substances and a high concentration of salts |
| JPS56112647A (en) * | 1980-02-12 | 1981-09-05 | Mitsui Petrochem Ind Ltd | Measuring method for amount of carbon and measuring device therefor |
| JP2001318057A (en) * | 2000-05-02 | 2001-11-16 | Mitsubishi Heavy Ind Ltd | Residual chlorine measuring method and its device |
| JP2004333280A (en) * | 2003-05-07 | 2004-11-25 | Mitsubishi Electric Corp | Concentration-measuring device |
| CN2706764Y (en) * | 2004-05-29 | 2005-06-29 | 徐滋秋 | Portable overall organic carbon tester |
| CN2749576Y (en) * | 2004-11-24 | 2006-01-04 | 尤尼柯（上海）仪器有限公司 | Horizontal rotor |
| CN2826430Y (en) * | 2005-08-19 | 2006-10-11 | 徐滋秋 | Laboratory total organic carbon determinator |
| WO2009125493A1 (en) * | 2008-04-11 | 2009-10-15 | 株式会社島津製作所 | Total organic carbon analyzer |
| CN201343453Y (en) * | 2008-12-30 | 2009-11-11 | 徐滋秋 | Automatic continuous measuring and controlling instrument for ultraviolet-oxidized water online temperature/electric conductance/total organic carbon |
| CN101587093A (en) * | 2008-05-23 | 2009-11-25 | 上海宝钢工业检测公司 | Method for measuring content of chloridion in wet flat liquid |
| CN202119742U (en) * | 2011-06-14 | 2012-01-18 | 曹余勤 | Chemical oxygen demand (COD)/total organic carbon (TOC)/twisted nematic (TN) online automatic monitor using high temperature burning oxidation method |
| CN102564823A (en) * | 2011-12-22 | 2012-07-11 | 烟台大学 | Device and method for continuously determining total organic carbon (TOC) concentration of sea water and high-salinity waste water |
| CN102590318A (en) * | 2012-02-24 | 2012-07-18 | 深圳市特种设备安全检验研究院 | Method and device for continuously analyzing pH value, phenolphthalein end-point alkalinity, total alkalinity and chloridion concentration |
| CN102879452A (en) * | 2012-09-21 | 2013-01-16 | 贵州红林机械有限公司 | Method for determining content of micro chlorine ions in surface treatment solution |
| CN104458366A (en) * | 2014-09-23 | 2015-03-25 | 浙江大学宁波理工学院 | Method for grading size of moisture soil by utilizing horizontal rotor centrifugal machine |
| CN104730266A (en) * | 2015-03-31 | 2015-06-24 | 烟台大学 | Method and instrument for synchronous and continuous real-time determination of total organic carbon and total nitrogen |
| CN104764740A (en) * | 2015-03-31 | 2015-07-08 | 烟台大学 | Method and instrument for synchronously, continuously and automatically measuring total organic carbon and total phosphorus |
-
2015
- 2015-11-08 CN CN201510758412.6A patent/CN105675831A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4248598A (en) * | 1978-05-30 | 1981-02-03 | Blunck Otto H | Process and apparatus for the determination of the contents of organically bound carbon in water containing organic substances and a high concentration of salts |
| JPS56112647A (en) * | 1980-02-12 | 1981-09-05 | Mitsui Petrochem Ind Ltd | Measuring method for amount of carbon and measuring device therefor |
| JP2001318057A (en) * | 2000-05-02 | 2001-11-16 | Mitsubishi Heavy Ind Ltd | Residual chlorine measuring method and its device |
| JP2004333280A (en) * | 2003-05-07 | 2004-11-25 | Mitsubishi Electric Corp | Concentration-measuring device |
| CN2706764Y (en) * | 2004-05-29 | 2005-06-29 | 徐滋秋 | Portable overall organic carbon tester |
| CN2749576Y (en) * | 2004-11-24 | 2006-01-04 | 尤尼柯（上海）仪器有限公司 | Horizontal rotor |
| CN2826430Y (en) * | 2005-08-19 | 2006-10-11 | 徐滋秋 | Laboratory total organic carbon determinator |
| WO2009125493A1 (en) * | 2008-04-11 | 2009-10-15 | 株式会社島津製作所 | Total organic carbon analyzer |
| CN101587093A (en) * | 2008-05-23 | 2009-11-25 | 上海宝钢工业检测公司 | Method for measuring content of chloridion in wet flat liquid |
| CN201343453Y (en) * | 2008-12-30 | 2009-11-11 | 徐滋秋 | Automatic continuous measuring and controlling instrument for ultraviolet-oxidized water online temperature/electric conductance/total organic carbon |
| CN202119742U (en) * | 2011-06-14 | 2012-01-18 | 曹余勤 | Chemical oxygen demand (COD)/total organic carbon (TOC)/twisted nematic (TN) online automatic monitor using high temperature burning oxidation method |
| CN102564823A (en) * | 2011-12-22 | 2012-07-11 | 烟台大学 | Device and method for continuously determining total organic carbon (TOC) concentration of sea water and high-salinity waste water |
| CN102590318A (en) * | 2012-02-24 | 2012-07-18 | 深圳市特种设备安全检验研究院 | Method and device for continuously analyzing pH value, phenolphthalein end-point alkalinity, total alkalinity and chloridion concentration |
| CN102879452A (en) * | 2012-09-21 | 2013-01-16 | 贵州红林机械有限公司 | Method for determining content of micro chlorine ions in surface treatment solution |
| CN104458366A (en) * | 2014-09-23 | 2015-03-25 | 浙江大学宁波理工学院 | Method for grading size of moisture soil by utilizing horizontal rotor centrifugal machine |
| CN104730266A (en) * | 2015-03-31 | 2015-06-24 | 烟台大学 | Method and instrument for synchronous and continuous real-time determination of total organic carbon and total nitrogen |
| CN104764740A (en) * | 2015-03-31 | 2015-07-08 | 烟台大学 | Method and instrument for synchronously, continuously and automatically measuring total organic carbon and total phosphorus |
Non-Patent Citations (7)
| Title |
|---|
| 刘娟等: ""高氯废水COD 测定方法的探究"", 《工业水处理》 * |
| 占新华等: ""土壤溶液和水体中水溶性有机碳的比色测定"", 《中国环境科学》 * |
| 孙玉兰等: ""氯离子的电位滴定研究"", 《海河水利》 * |
| 易春叶等: ""高氯废水COD 测定中消除Cl-干扰的方法探讨"", 《广东化工》 * |
| 李东权等: ""某化工厂高氯废水COD测定方法的实验研究"", 《铁路节能环保与安全卫生》 * |
| 李芳等: ""自动电位滴定仪测定水中氯离子的探讨"", 《腐蚀研究》 * |
| 辽宁省环境科学学会: "《资源生态并举环境发展共生-辽宁省环境科学学会2009年学术年会论文集》", 31 July 2009 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106290316A (en) * | 2016-08-16 | 2017-01-04 | 湖北兴发化工集团股份有限公司 | A kind of analysis method of Dimethyldichlorosilane hydrolysate intermediate ion |
| CN106338945A (en) * | 2016-10-14 | 2017-01-18 | 王杨 | Intelligent electronic semi-finished product detection apparatus |
| CN112461991A (en) * | 2019-09-06 | 2021-03-09 | 荆门市格林美新材料有限公司 | Method and device for rapidly detecting metal yield of battery material |
| WO2021231073A1 (en) * | 2020-05-12 | 2021-11-18 | University Of Washington | Apparatus and method for measurement of halogens in samples |
| CN112526099A (en) * | 2020-12-11 | 2021-03-19 | 江苏源泉智能装备科技有限公司 | High-chlorine wastewater COD detection device and method |
| CN112526099B (en) * | 2020-12-11 | 2022-11-01 | 江苏恒源环境检测股份有限公司 | High-chlorine wastewater COD detection device and method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105675831A (en) | Apparatus and method for measuring chlorine ion and total organic carbon in water | |
| CN201488944U (en) | Total organic carbon (TOC) analyzer | |
| EP0897538B1 (en) | Method and apparatus for the measurement of dissolved carbon in deionized water | |
| CN101907558A (en) | Total organic carbon online analyzer and method for analyzing total organic carbon | |
| CN103499558A (en) | System and method for determining mercury concentration in water | |
| CN102980860B (en) | Full-automatic quick measurement system and method for water quality hexavalent chromium | |
| CN101672775A (en) | Seawater total organic carbon automatic on-line monitoring instrument | |
| Van Staden et al. | Determination of sulphate in natural waters and industrial effluents by sequential injection analysis | |
| Buffle et al. | Permeation liquid membranes for field analysis and speciation of trace compounds in waters. | |
| CN105675832A (en) | Apparatus and method for measuring total organic carbon (TOC) | |
| CN105675763A (en) | Multifunctional chromatographic apparatus and method for measuring chloridion and total organic carbon | |
| CN104483280A (en) | Method for rapidly detecting ammonia nitrogen removal rate | |
| CN102564823A (en) | Device and method for continuously determining total organic carbon (TOC) concentration of sea water and high-salinity waste water | |
| JP2000111547A (en) | Fluid specimen measurement system | |
| CN201555755U (en) | Device for automatically monitoring total organic carbon in seawater | |
| CN110658139A (en) | Permanganate index analysis system | |
| CN211122512U (en) | Permanganate index analysis system | |
| CN101696938A (en) | Method for online monitoring of copper ions in water through flow injection | |
| Wang et al. | Chemiluminescence determination of nitrogen oxide in air with a sequential injection method | |
| CN207689371U (en) | Ultralow memory effect atomic fluorescence trace mercury vapourmeter is miniaturized | |
| Xie et al. | Implementation of an automatic and miniature on-line multi-parameter water quality monitoring system and experimental determination of chemical oxygen demand and ammonia-nitrogen | |
| Kojlo et al. | Flow-injection biamperometry of phenol | |
| CN210269598U (en) | Chemical analysis system for total nitrogen | |
| CN208872578U (en) | A kind of high-chlorine and high-calcium COD in Wastewater system | |
| JP2017223583A (en) | Water Quality Analyzer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160615 |
|
| RJ01 | Rejection of invention patent application after publication |